Adhesion-promoting composition for textile material and associated reinforcing textile material

Abstract

To provide an adhesion-promoting composition for a textile material and an associated reinforcing textile material.SOLUTION: The invention relates to an adhesion-promoting composition for a textile material, comprising a salt of lignosulphonate, an epoxy curing agent for the salt, comprising at least two epoxide units, and an elastomer latex. The lignosulphonate salt can be a lignosulphonate of sodium, potassium, magnesium, ammonium or calcium. The invention also relates to the use of such a composition for providing a reinforcing textile material with adhesive properties, in relation to a rubber material, to a reinforcing textile material, particularly a textile structure, yarn or cord, at least partially coated and / or impregnated with the composition, and to a part made of rubber or a part comprising a rubber material, in which the rubber comprises at least one reinforcing textile material, on the surface thereof and / or integrated into the rubber material.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an adhesive or bonding composition for textiles, and more particularly to a composition for adhering textiles to rubber. More particularly, the present invention relates to the field of use in belts, pipes, tires, air springs, and more generally, any part or article containing rubber or rubber parts that contain reinforcing textiles on the surface and / or in the depth (in the mass). Thus, the present invention also relates to reinforced textiles coated with this adhesive and to parts or articles incorporating this adhesive both on the surface and in the depth.

Background Art

[0002] Taking the example of a transmission belt, the textile reinforcement must first and foremost guarantee the dimensional stability of the belt. For this purpose, the reinforcement is required to have specific mechanical properties in various environments. In order to guarantee the required properties and particularly avoid the risk of delamination, the textile reinforcement must adhere to the rubber of the belt. The reinforcement may come into contact with one rubber or a plurality of different rubbers. In order to enable excellent compatibility with the rubber, the reinforcement is generally treated with an adhesive. The reinforcement may also be required to have more complex properties. For example, the edges of the reinforcement must be easy to cut while not fraying when cut and exposed on the side of the belt. In order to guarantee these other properties, other types of treatment can be applied to the yarn.

[0003] In order to obtain all of these properties, it is necessary to provide the yarn with a certain structure, particularly a structure in the form of a cord, and to provide a plurality of chemical and heat treatments.

[0004] Since a plurality of different treatments are applied to the textile reinforcement, it is essential to guarantee the compatibility between the adhesive and the reinforcement, between the rubber and the reinforcement, and between the other treatments applied to the reinforcement.

[0005] The main purpose of the chemical treatment is to adhere a given reinforcing material to the various rubbers with which it may come into contact. The treatments vary, as do the types of reinforcing materials present [such as glass, aramid, polyamide (PA), polyethylene terephthalate (PET), etc.] and the number of rubbers.

[0006] At the heart of the treatment for adhering reinforced textiles to rubber is the so-called resorcinol formaldehyde latex, i.e., the RFL treatment. This is a system that involves mixing a latex (a colloidal aqueous dispersion of an elastomer or polymer) with a thermosetting resin of the phenoplast or aminoplast type. This system has a history, was widely developed in the 1970s, and continues to be a selective treatment. Despite many attempts to replace this treatment, to date, it has never been possible to provide a wide-ranging solution to achieve equivalent performance. This is fully optimized to obtain maximum static adhesion, i.e., adhesion without dynamic stress.

[0007] The heat treatment affects not only the chemical properties (adhesiveness) but also the mechanical properties in the case of synthetic reinforcing materials. This affects, among other things, the shrinkage properties. The treatment in the oven results from a compromise between maintaining the mechanical properties and cross-linking the adhesive.

[0008] Therefore, for all these reasons, a new treatment must be able to adapt to the current treatment conditions in order to guarantee the mechanical properties. However, an adhesive that enables treatment at a lower temperature potentially offers new advantageous properties in certain fields of use and shows advantageous energy aspects.

[0009] However, in order to improve the adhesion performance or provide abrasion resistance, it may be necessary to apply up to four different treatments continuously to the textile, including treatment with RFL. These are the following treatments: 1) Core treatment of the yarn that captures the filaments within the matrix and enables the filaments to be blocked therebetween. Thus, this provides fray resistance and imparts stiffness to the yarn. 2) Pre-activation to improve adhesion. 3) RFL treatment in one or two layers. 4) Overcoat in the form of a commercially available adhesion promoter or elastomer solution (sometimes called a cement bond).

[0010] Thus, it is also equally preferable that no problems occur with the functionality of various chemical and thermal (or more generally, physical) treatments commonly used for various applications due to any changes in formulation.

[0011] Taking into account all the constraints mentioned above, the RFL treatment has been recognized as a selected treatment that enables adhesion between textiles and rubber. The phenomena involved in adhesion are exerted during the vulcanization of rubber parts, while the RFL treatment itself can be applied to textiles several months in advance. For this reason, in many cases the term "bonding" treatment is used, and the term "adhesion" is rather reserved for indicating the adhesion state. In RFL, the latex is generally an aqueous colloidal dispersion of an elastomer or polymer that is similar in nature to the rubber to be bonded. However, these latexes do not have actual mechanical properties as they are. To ensure the strength of the system, a thermosetting (thermosetting) resin is added. This is an RF resin made from resorcinol and formaldehyde. Through its polarity, this provides excellent adhesion to the textile. It forms a mesh, within which the latex is trapped, rigidifying the system. This mesh allows the diffusion of elastomer chains within the matrix and continues to have sufficient flexibility to provide excellent adhesion to the rubber (entanglement, molecular interactions and possibly co-crosslinking during vulcanization).

[0012] RFL contains formalin and resorcinol, which are currently known as substances suspected of being carcinogenic. Therefore, it seems advantageous to find alternatives to this formalin and resorcinol, or to the entire RFL composition. Due to the complex properties of RFL repeatedly described above, from both the perspective of its implementation and the usage characteristics of the end products encompassing it, attempting to discover alternative solutions has actually become difficult. It seems even more advantageous to find such a solution that not only provides more than an alternative but also enhances performance. These are the problems that the inventors have set out to overcome.

Summary of the Invention

Problems to be Solved by the Invention

[0013] Therefore, an object of the present invention is to provide a new adhesive solution that enables, in particular in known applications of RFL, to replace RFL, provide a performance level close to or even better than it, and moreover achieve this using components that are acceptable under favorable economic conditions related to sustainable development.

[0014] Lignosulfonates are provided as natural adhesives, as short fiber binders for making mats (non-woven) in combination with lignosulfonate hardeners, or as adhesives in multi-layer wood-based products. These have never been proposed as alternative compositions to RFL, and there is no indication that lignosulfonates are suitable for developing adhesive formulations to guarantee the bond with rubber and provide sufficient mechanical performance. Similarly, as described in Patent Documents JP-A-2002-226812 and JP-A-2001-234143, they are also used as surfactants in compositions that do not contain hardeners.

Means for Solving the Problems

[0015] Accordingly, the subject of the present invention is a composition comprising (or based on, consisting essentially of, or composed of) lignosulfonate, an epoxy hardener for this salt, and a polymer latex, in particular an elastomer latex. Specifically, this is an adhesive composition or a bonding composition for textiles.

[0016] The term "epoxy hardener" used in the present invention is understood to mean a compound containing at least two epoxy units or oxacyclopropane or -CH-CH2-O rings. This compound can undergo an addition reaction with components such as alcohols by opening the epoxy ring. The presence of two epoxy units enables a reaction with two units containing alcohol, and thus a polymerization reaction, also known as crosslinking. Therefore, the epoxy hardener according to the present invention is a crosslinking agent for crosslinking lignosulfonate.

[0017] The subject of the present invention is also a composition for textiles, specifically an adhesive or a bonding composition, obtained or obtainable by mixing lignosulfonate, an epoxy hardener for this salt, and a polymer latex, in particular an elastomer latex. In one embodiment, the composition is obtained or obtainable by mixing lignosulfonate and an epoxy hardener for this salt in a basic medium and then adding a polymer latex, in particular an elastomer latex; or by mixing lignosulfonate and a polymer latex, in particular an elastomer latex, in a basic medium and then adding an epoxy hardener for this salt.

[0018] In one embodiment, the composition contains a product obtained as a result of the reaction between lignosulfonate and an epoxy hardener for this salt in a basic medium.

[0019] The composition can be a bonding composition used for adhering textiles to rubber or similar materials. These compositions are compositions applicable onto a substrate, such as in particular textiles, in particular the textiles according to the present invention. The present invention likewise relates to a method for its preparation.

[0020] The subject of the present invention also lies in these compositions which are dried and cured after undergoing a suitable treatment process such as heat treatment. The term "drying" is understood to mean the evaporation of water or volatile substances. The term "curing" is understood to mean any polymerization or crosslinking reaction, either total or partial, of compounds present in the composition and having the ability to react under the applied treatment conditions, including conditions that do not require heat treatment. These dried and cured compositions are then generally associated with a substrate, such as in particular textiles, in particular the textiles according to the present invention, or rubber parts including these textiles. The term "associated" is used to indicate that the composition impregnates the textile, coats the textile or impregnates and coats the textile. The coating may be continuous or discontinuous. The impregnation may be complete up to the core or partial.

[0021] The subject of the present invention also lies in a kit or set comprising a first composition containing lignosulfonate and polymalatex, in particular elastomalatex; and a second composition containing an epoxy hardener for the lignosulfonate. The first and second compositions are suitable for being mixed to form a bonding composition and are so intended, and then this bonding composition is applied onto textiles in the sense of the present invention.

[0022] The present invention likewise relates to an application method for applying the bonding composition according to the present invention in order to impart adhesion properties to reinforced textiles in relation to rubber and the like. This method includes drying and curing steps of the composition using a suitable treatment process such as heat treatment.

[0023] The present invention also relates to the use of the composition according to the invention or of the dried and cured bonding composition for imparting adhesion properties to reinforcing textiles in relation to, for example, rubber.

[0024] The present invention also relates to reinforcing textiles, in particular yarns, cords or textile structures, at least partially coated and / or impregnated with the bonding composition according to the invention, in particular in the dried and cured state.

[0025] The present invention also relates to articles or parts made of rubber (or similar materials) which contain rubber and incorporate at least one reinforcing textile according to the invention on the surface and / or inside of the rubber or rubber matrix, or articles or parts which contain parts made of rubber (or similar materials).

[0026] Other objects of the present invention will become apparent upon reading the following detailed description.

Embodiments for Carrying Out the Invention

[0027] Accordingly, a first object of the present invention is an adhesive or bonding composition for textiles, comprising (or based on, essentially consisting of, or consisting of) at least one lignosulfonate, at least one epoxy curing agent for this salt, and an elastomer latex.

[0028] Although not intended to be bound by theory, it is of course expected that lignosulfonates and epoxy hardeners of these salts will react together to form reaction products, whether or not the mixture is subjected to heat, such as heat treatment applied to the textile after coating and / or impregnating with the bonding composition. It is expected that when the compound is subjected to heat, the lignosulfonate will initiate a reaction with the epoxy hardener in a cross-linking reaction by adding a reactive unit of the lignosulfonate to the epoxy ring and opening the ring. This heat can be applied during a heat treatment process such as a heat treatment applied to the textile after coating and / or impregnating with the bonding composition. Since the epoxy hardener contains at least two epoxy units, a cross-linking reaction and thus the formation of a polymer or resin is expected. In one advantageous embodiment, the presence of a basic medium is expected to act favorably on this reaction. This reaction state is examined and explained in more detail in the first part of the examples. However, it cannot be excluded that one or more reaction mechanisms between the lignosulfonate and the epoxy occur during preparation or storage. The term "reaction product" is of course understood to mean the product of the reaction between the lignosulfonate and the epoxy hardener, excluding any additives that may be likely to enter the final composition.

[0029] This composition can in particular be obtained by a method which is likewise an object of the invention, by mixing the three components while stirring.

[0030] As exemplified in the examples, according to the first embodiment, lignosulfonate can be dissolved in water, and then the resulting solution can be mixed with latex and epoxy. This solubilization can be promoted by adding soda and / or ammonia-type agents and acting in a basic medium. According to one method, the lignosulfonate solution and latex are first mixed, and then the epoxy is added only afterwards. According to another method, the lignosulfonate solution and the epoxy curing agent are first mixed, and then the latex is added only afterwards. Thus, the foregoing constitutes two modes. Note that, unless otherwise indicated, the term "addition" may be understood to mean the addition of the first product to the second product, or vice versa.

[0031] In one embodiment of the preparation method, the lignosulfonate can be dissolved in water with stirring, and in the presence of an agent that makes the pH basic, the mixture is preferably stirred until complete solubilization is achieved. Then, the mixture is added to the latex with stirring, and then the curing agent is incorporated with stirring (preferably this curing agent is pre-dissolved or dispersed in water, for example, with vigorous stirring). According to one practical mode, the mixture of lignosulfonate and latex is added to a solution or dispersion of the epoxy curing agent. The mixing with the epoxy curing agent can be carried out following the preparation of the mixture of lignosulfonate and latex, or later, as in the case of a kit or set that is the subject of the present invention. The composition can be used as an immediately usable bonding composition or as a bonding composition that can be adjusted and diluted as required.

[0032] According to another embodiment of the method, it is possible to mix an aqueous solution of lignosulfonate and an epoxy curing agent and then add the mixture to the aqueous dispersion of the latex while stirring. According to one practical mode, the mixture of lignosulfonate and epoxy curing agent is added to the latex. Advantageously, the pH of the lignosulfonate solution or the solution of lignosulfonate and curing agent is adjusted to be basic, for example by adding sodium hydroxide and / or ammonia before incorporation of the latex. The composition can be used as a ready-to-use adhesive composition or as an adhesive composition that can be adjusted and diluted according to requirements.

[0033] The following features are applicable to various objects of the present invention.

[0034] The latex is preferably a basic aqueous dispersion of a polymer and / or an elastomer. Similarly, it is also possible to carry out according to the present invention at a neutral pH. The pH value to be carried out can in particular be the value mentioned below with respect to the pH of the composition.

[0035] The term "elastomer" is understood in particular to mean a polymer or copolymer having a glass transition temperature (Tv) of less than approximately 25°C. Elastomers are present in the rubber to be bonded and in the latex of the bonding composition. "Elastomer latex" is a colloidal aqueous dispersion of an elastomer.

[0036] The terms "rubber" or "elastomeric material" in this specification are understood to mean a vulcanized or crosslinked product prepared from either synthetic or natural elastomers or elastomeric rubbers with one or more types of fillers, reinforcing agents (such as carbon black, silica, kaolin, etc.), plasticizers, vulcanizing agents (such as sulfur, peroxides, metal oxides and necessary accelerators), and any other usual additives for the application in question (such as those for facilitating the implementation of protection against oxygen, ozone, heat, flame, UV). The present invention relates to both synthetic and natural rubbers. The rubber formulated on the basis of an elastomer has its resulting Tv is a material that is lower than the service temperature, operating temperature, or application / utilization temperature of a mechanical part or assembly formed using one or more rubbers.

[0037] Lignosulfonates are by-products obtained as a result of wood treatment for the production of paper pulp according to a method known as the "acid bisulfite cooking process," particularly in wood processing. This method using bisulfite enables the corresponding lignosulfonates to be obtained depending on the nature of the counterion used. These lignosulfonates can similarly be derived from the methods intended to produce them from wood.

[0038] Preferably, in the bonding composition, the lignosulfonate can be a sodium, potassium, magnesium, ammonium, or calcium salt.

[0039] In one exemplary embodiment, a lignosulfonate prepared from French poplar, for example, from the Landes department (France) by the bisulfite process is used.

[0040] Preferably, the bonding composition does not contain formaldehyde or formalin. Preferably, the bonding composition does not contain resorcinol. Preferably, the bonding composition does not contain formaldehyde or formalin and resorcinol. Preferably, the bonding composition does not contain an organic solvent. The bonding composition uses water as a solvent and its pH can be adjusted as needed.

[0041] The epoxy hardener according to the present invention is a polyepoxy compound containing at least two epoxides or epoxy groups or units. Specifically, it refers to those containing an average of two or more glycidyl or methyl-glycidyl radicals carried by a heteroatom, preferably an oxygen or nitrogen atom, more specifically an oxygen atom; or those containing an average of two or more epoxy-cyclo-hexyl groups. It is possible to use a plurality of different compounds from the following list.

[0042] Examples of the curing agent include, in particular, the following: - diglycidyl or polyglycidyl ethers of aliphatic polyols; - diglycidyl or polyglycidyl ethers of polyfunctional phenols; - polyglycidyl ethers of condensation products of formaldehyde and phenol obtained under acidic conditions; - di- or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids; - compounds containing an epoxycyclohexyl group; - polyepoxy compounds obtained as a result of the epoxidation of olefinically unsaturated compounds.

[0043] Specific examples include the following: - diglycidyl or polyglycidyl ethers of aliphatic polyols, such as 1,4-butanediol; 1,6-hexanediol; 1,2,6-hexanetriol; glycerol; neopentyl glycol; ethylene glycol; triethylene glycol; 1,2-propylene glycol or polyalkylene glycols, such as polypropylene glycol; or derivatives of polyalkylene glycols, such as polypropylene glycol; - Diglycidyl or polyglycidyl ethers of polyfunctional phenols, such as 2,2-bis(4-hydroxyphenyl)propane (or BPA); 2,2-bis(4-hydroxyphenyl)hexafluoropropane (or BPA-F); 1,1-bis(4-hydroxyphenyl)-1-phenyl-ethane (or BPA-P); 2,2-bis(4-hydroxyphenyl)butane (BPB); bis(4-hydroxyphenyl)diphenylmethane (or BPBP); 2,2-bis(3-methyl-4-hydroxyphenyl)propane (or BPC); bis(4-hydroxyphenyl)-2,2-dichloroethylene (or BPCII); bis(4-hydroxyphenyl)methane (or BPF); 4,4'-(9H-fluorene-9-ylidene)bisphenol (or BPFL); 2,2-bis(4-hydroxy-3-isopropylphenyl)propane (or BPG); 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene (or BPM); 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), etc.; - Polyglycidyl ethers of condensation products of phenol with formaldehyde obtained under acidic conditions, i.e., novolaks of phenol and novolaks of cresol, etc.; - Ethers of compounds containing epoxycyclohexyl groups, such as 3,4-epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate; epoxy-8,9(epoxy-3,4 cyclohexyl)-3-dioxa-2,4 spiro5.5 undecane; and bis(3,4-epoxycyclohexylmethyl) adipate, etc.; - Di- or polyglycidyl esters of polycarboxylic acids such as phthalic acid, terephthalic acid, A-tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, oxalic acid, succinic acid, glutaric acid, dimerized linolenic acid, etc.

[0044] It is understood that the epoxy curing agent can be specifically selected from among the compounds listed below, where the composition can include one or more of them, particularly two of them: - 1,4-Butanediol diglycidyl ether (diglycidyl ether of an aliphatic polyol) - 2,2-Bis(4-hydroxyphenyl)propane diglycidyl ether (diglycidyl ether of a polyfunctional phenol) - Diglycidyl 1,2-cyclohexanedicarboxylate (di- or poly-glycidyl ester of a polycarboxylic acid) - 3,4-Epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate (compound containing an epoxycyclohexyl group) - 1,6-Hexanediol diglycidyl ether (diglycidyl ether of an aliphatic polyol) - Glycerol diglycidyl ether (diglycidyl ether of an aliphatic polyol) - Glycerol triglycidyl ether (poly-glycidyl ether of an aliphatic polyol) - A mixture of glycerol diglycidyl ether and glycerol triglycidyl ether, commercially available from Raschig as, for example, product number GE100 (diglycidyl ether of an aliphatic polyol). - A novolac epoxy resin, commercially available from HUNTSMAN as, for example, product number Araldite PZ323 (poly-glycidyl ether of a condensation product of formaldehyde and phenol).

[0045] Epoxy curing agents may similarly be selected from heterocyclic amines, amides, and N-glycidyl derivatives of nitrogen-containing bases, such as N,N-diglycidyl-aniline; N,N-diglycidyl-toluidine; N,N,N’,N’-tetrakis-glycidyl bis(4-aminophenyl)-methane; the triglycidyl derivative of 4-hydroxyaniline; triglycidyl isocyanurate; N,N’-diglycidyl-ethylene-urea; N,N’-diglycidyl-5,5-dimethylhydantoin; N,N’-diglycidyl-isopropyl-5 hydantoin; and N,N’-diglycidyl-5,5-dimethyl-6-isopropyl-5,6-dihydro-uracil.

[0046] The latex can advantageously be a latex of acrylonitrile / carboxylated butadiene copolymer (XNBR), a latex of acrylonitrile / hydrogenated butadiene (HNBR), a latex of chlorosulfonated polyethylene (CSM), a latex of styrene-butadiene-vinylpyridine copolymer (VPSBR), a styrene-butadiene copolymer latex (SBR), an acrylonitrile / butadiene copolymer latex (NBR), a polybutadiene latex (BR), a chlorobutadiene latex (CR), a natural rubber latex (NR), a polyurethane latex or a mixture of at least two of them.

[0047] The weight content of the dry matter of the composition can be, in particular, approximately 2 to approximately 38%, in particular approximately 4 to approximately 30%, more particularly approximately 7 to approximately 25%.

[0048] The composition according to the invention can in particular contain approximately 40 to approximately 95% by weight, preferably approximately 55 to approximately 90% by weight or approximately 40 to approximately 60, 70, 80 or 90% by weight of elastomer in relation to the composition.

[0049] Unless otherwise indicated, the composition is provided as dry matter.

[0050] In the composition, the mass ratio of hardener / lignosulfonate can be, in particular, approximately 0.01 to approximately 5, more particularly approximately 0.03 to approximately 1, typically approximately 0.05 to approximately 0.5. Depending on the pair of hardener and lignosulfonate selected, it may prove possible to have lower or higher values, and this parameter can be determined by a person skilled in the art based on this specification.

[0051] In the composition, the mass ratio of [hardener + lignosulfonate] / latex can be, in particular, approximately 0.05 to approximately 0.6, more particularly approximately 0.15 to approximately 0.5. Depending on the compounds selected in combination, it may prove possible to have lower or higher values, and this parameter can be determined by a person skilled in the art based on this specification.

[0052] According to an advantageous feature, the composition has a neutral or basic pH, in particular a pH of approximately 7 to approximately 13, in particular approximately 9 to approximately 13. For this purpose, the composition can contain additives that enable adjustment of the pH, such as soda, for example.

[0053] The composition contains water of the elastomer latex. Further water can be added, for example by impregnation, to make the applicable composition have sufficient fluidity for conventional applications.

[0054] The composition can likewise contain additives, in particular at a content of approximately 0.01 or 0.1% to approximately 50% by dry mass. The composition contains in particular bonding or adhesion promoters soluble in an aqueous medium (such as silanes, blocked isocyanates), surfactants, dispersants, defoamers, waxes (such as microcrystalline hydrocarbon waxes in emulsion form), fillers (such as carbon black, silica), colorants, metal oxides (such as zinc oxide ZnO), elastomer crosslinking agents, anti-UV agents, anti-ozone agents, and heat protection agents. These agents are additives conventionally used in RFL formulations. They are compatible with the adhesives that are the goal of the present invention.

[0055] In one embodiment, the bonding composition for textiles consists essentially of lignosulfonate, an epoxy curing agent for this salt, and an elastomer latex, and can contain one or more additives, in particular one or more of the adhesives mentioned in the previous paragraph. Advantageously, the composition according to the present invention does not contain any conventional catalysts or curing agents for compounds containing epoxy groups or units, such as triethylenetriamine (TETA) and triethylamine (TEA).

[0056] The viscosity of the bonding composition is measured at 23°C using a Brookfield viscometer, for example, for a ULA module suitable for low viscosity. As detailed in the examples, the viscosity can be adjusted, in particular, by adjusting the water content. The viscosity can be adjusted to obtain the desired level to enable excellent application to the textile in the coating process or impregnation process used. In the case of impregnation by immersion, this viscosity can be particularly approximately 1 to approximately 10, typically approximately 1 to approximately 5 Cp or mPa.s.

[0057] The composition according to the present invention can be applied to any textile. The term "textile" in the context of the present invention is understood to mean any assembly of continuous monofilament yarns, continuous multifilament yarns, staple fibers, monofilaments and / or multifilament continuous yarns or chopped yarns, in particular wicks, cords formed from such yarns by conventional twisting techniques and, in particular, "textile structures" formed from assemblies of twisted or cabled yarns in the form of fabrics, grids, etc. The textiles of the present invention treated with the composition according to the present invention are referred to by the expression "reinforced textiles".

[0058] The textile can be essentially organic or inorganic. Examples of textile types include, in particular, glass (especially E-glass or high-modulus glass), basalt, carbon, aramid (meta or para), polyvinyl alcohol, cellulose, high-density polyethylene (HDPE), polyester (especially polyethylene terephthalate, PET), polyamide (PA, especially PA4.6, PA6.6, PA6), acrylic, hybrid (both cabled aramid yarn + nylon yarn; both cabled acrylic + glass + copper), etc. If the textile is a cord or textile structure of a plurality of yarns, the yarns can all be essentially organic or inorganic, or the cord or textile structure can include both organic and inorganic types of yarns.

[0059] The subject of the present invention also lies in the application method or use of the bonding composition according to the present invention for imparting bonding properties to such textiles, especially in relation to elastomeric materials. This use can be misused in the term of the bonding method of the textile according to the present invention. This use or method includes the steps of applying the composition to the textile (yarn, cord, textile structure) and then drying it. This application can be carried out by methods used in the industry for coating, especially by impregnation, as described below. The selection of latex and thus the elastomer as a constituent preferably tends to deviate towards a formulation similar to the nature of the elastomer constituting the rubber to be treated.

[0060] In one embodiment, the impregnation of the textile is carried out by "dipping" into a tank containing the adhesive preparation.

[0061] Yarns, cords and cables can be subjected to either direct immersion in a tank or impregnation using a kiss roll, in particular for applying the bonding composition. After the immersion or impregnation, the excess wet preparation is preferably removed by physical compression between porous supports such as, for example, a press (padding), a spinneret die, suction or a foam. After the immersion or impregnation and, optionally, the final removal of the excess preparation, the drying and heat curing of the bonding composition are then carried out. The impregnated textile thus coated can be passed through an oven to enable the drying and crosslinking of the bonding composition. After removal from the oven, the textile can again undergo the impregnation step (impregnation by kiss roll or by dipping), and then pass through the oven, and these steps can be repeated, especially up to a total of 4 impregnations (2, 3 or 4 times).

[0062] In another impregnation method that is particularly suitable for mineral fibers (such as glass, basalt, carbon, etc.), a splitting system composed of combs and / or "pigtails" can be used before impregnating the multifilament yarn. This enables maximum fibrillation of the multifilament yarn to promote thorough impregnation. After impregnation or immersion using the kiss roll as described above, the excess wet preparation is preferably removed by physical compression between porous supports such as, for example, pressing (padding), suction, or foams. After impregnation or immersion, and in some cases the final removal of the excess preparation, drying and heat curing of the bonding composition are then carried out. The impregnated yarn thus coated can be passed through an oven to enable drying and crosslinking of the bonding composition. After removal from the oven, the yarn can again undergo the impregnation step (by impregnation with a kiss roll or by immersion), and then pass through the oven, and these steps can be repeated, especially up to a total of 4 impregnations (2, 3, or 4 times).

[0063] After impregnation, drying, and heat curing of the yarn, the yarn is then twisted in line. Cabling is preferably carried out on the already processed yarn, but it is equally possible to carry out cabling first and then the impregnation, drying, and heat curing steps. In various different methods, the speed can be in the range of 1 m / min to 150 m / min, and the temperature of the oven is in the range of 30°C to 350°C, more specifically 100 to 300°C, and even more specifically 140 to 220°C. Mechanical tension can also be applied to the textile throughout the process.

[0064] One embodiment relates to the production of textile reinforcement materials for incorporation into assemblies such as drive belts or conveyor belts. For this purpose, for example, polyamide cords such as PA4-6 are constructed by twisting and then cabling. The resulting cords may optionally and advantageously be treated by a first core impregnation process intended to block the filaments from each other and impart fray resistance to the yarn, and thus also impart stiffness to the yarn. This can be done using a solution of methylene diphenyl diisocyanate in toluene, and the impregnated cords are then subjected to drying and heat curing in an oven. The cords are then impregnated in a tank containing the adhesive composition of the present invention and then dried and heat cured in an oven.

[0065] Another embodiment relates to the production of textile reinforcement materials for incorporation into profiles and seals such as window or door seals. Such reinforcement materials may in particular be made of glass yarns containing a glass fiber sizing agent with which the adhesive composition should be compatible. It is possible to start with glass yarns (especially E-glass), which are subjected to a untwisting process (as described above) and an impregnation process in a tank containing the bonding composition of the present invention. The impregnated yarns are subjected to drying and heat curing in an oven. After removal from the oven, the yarns are subjected to a twisting operation. A plurality, for example three, impregnated twisted yarns can then be cabled together.

[0066] Another embodiment relates to the production of textile reinforcement materials designed to serve as braids, coils, wraps or knit reinforcements within brake pipes. It is possible to start with yarns made of organic materials such as polyethylene terephthalate (PET), high density polyethylene (HDPE), or polyamide. Preferably, twisting is applied to them. Preferably the twisted yarns are subjected to treatment by impregnation in the bonding composition of the present invention, followed by drying and heat curing in an oven.

[0067] As a variant of this embodiment, it is possible to build the cord starting from similar yarns and then using the steps of successive twisting and subsequent cabling. The resulting cord is treated by a first core impregnation process intended to block the filaments from each other and impart fraying resistance to the yarn, and thus also give rigidity to the yarn, for example by using a solution of methylene diphenyl diisocyanate in toluene; the cord is then subjected to drying and thermosetting in an oven. The resulting cord is then treated by impregnation in the bonding composition of the invention and then drying and thermosetting in an oven.

[0068] Other features related to use or method will become apparent upon reading the remaining description.

[0069] The subject of the present invention is also in reinforced textiles coated and / or impregnated with the bonding composition according to the invention. The object of the present invention is in particular a reinforced textile which can be obtained by coating and / or impregnating with the bonding composition described herein and implementing the method described herein. It also relates to a textile treatment method for treating textiles for the purpose of producing reinforced textiles by applying an adhesive composition to said textiles.

[0070] The subject of the present invention is in particular in yarns coated and / or impregnated with the bonding composition according to the invention. The yarn may be a twisted yarn, and the twisting may be carried out before or after the application of the composition and its drying and / or curing. If the yarn is multifilament, it can be completely impregnated up to the core, which could be obtained, if necessary, by splitting the yarn before impregnation with the composition (separation of the filaments by means known to those skilled in the art). This yarn may in particular contain or be coated with the cured bonding composition (dried and / or crosslinked).

[0071] The subject of the present invention is also in cords coated and / or impregnated with the bonding composition according to the invention. This cord may in particular contain a cured bonding composition (dried and / or crosslinked) or may be coated with this cured bonding composition.

[0072] The cord may be formed from at least two yarns not coated or impregnated with the adhesive composition. Generally each yarn is first twisted, then the yarns are cabled (assembled together and twisted in a direction opposite to the direction of twisting of the basic yarns), and then the cord is impregnated with the adhesive composition which is cured after application.

[0073] The cord may also be formed by the assembly of at least two yarns coated or impregnated with the adhesive composition. Generally each yarn is twisted after the setting of the composition, then the yarns are cabled (assembled together and twisted in a direction opposite to the direction of twisting of the basic yarns); it is possible to provide a coating process for the cord combined with other treatment processes ("overcoat" or "topcoat") and its drying.

[0074] The subject of the present invention is also in textile structures formed by assembling yarns by gluing or joining in the case of known techniques such as weaving or grids. These textile structures are coated or impregnated with the composition of the invention, and the present invention encompasses such textile structures coated with a cured bonding composition.

[0075] The bonding composition can be applied to the textiles in the sense of the present invention by a method used for RFL. Impregnation, direct dipping or kiss roll should be selected first.

[0076] The subject of the present invention is also an article or part made of rubber (or comprising a rubber part), including at least one reinforcing textile according to the present invention, in particular a yarn, cord and / or textile structure. This reinforcing textile can in particular be applied to the surface of the article or part and / or integrated into the interior of the article or part.

[0077] As previously described, rubber is a vulcanizable formulation based on natural or synthetic elastomers, such as vulcanized (crosslinked) natural rubber (NR or polyisoprene), or synthetic, vulcanized (crosslinked) rubber. Examples of synthetic rubbers include polybutadiene (BR), polyurethane (AU or EU), polychloroprene (CR), silicone (VMQ, PVMQ) and fluorosilicone (FVMQ), ethylene-propylene-diene monomer (EPDM), butadiene-acrylonitrile copolymer (NBR, i.e. nitrile butadiene rubber), hydrogenated butadiene-acrylonitrile copolymer (HNBR), styrene-butadiene copolymer (SBR), epichlorohydrin (ECO or CO), butyl (IIR), bromobutyl (BIIR), chlorobutyl (CIIR), chlorinated polyethylene (CM), chlorosulfonated polyethylene (CSM), carboxylated nitrile butadiene acrylonitrile (XNBR), copolymer of ethylene and methyl acrylate (AEM), copolymer of ethylene and vinyl acetate (EVM and EVA), polyacrylate (ACM), fluororubber (FKM), perfluororubber (FFKM).

[0078] Rubber may also be a vulcanizable formulation based on a mixture or cut of such elastomeric rubbers.

[0079] Rubber can also be a formulation based on thermoplastic elastomers (so-called "physically crosslinked" elastomers, such as SBS, styrene-butadiene-styrene block, etc.).

[0080] The subject of the present invention is, in particular, a reinforced textile bonded according to the present invention [embedded within the mass made of elastomer or rubber or in a state flush with the surface], such as individual or cabled or otherwise assembled in the form of a textile structure, or one or more yarns belonging to two or more of these categories. The article or part made of elastomer or rubber includes

[0081] The term "bonded" is understood in particular to indicate that the reinforced textile contains a cured (dried and / or crosslinked) bonding composition or is coated with a cured bonding composition.

[0082] The subject of the present invention is also an article or part made of elastomer or rubber, which contains one or more yarns embedded within the mass made of elastomer or rubber, which may be individual or cabled or assembled in the form of a textile structure, or belonging to two or more of these categories, and in addition, a textile structure according to the present invention bonded or adhered to at least one surface of this elastomer or rubber material, where these reinforced textiles are adhered according to the present invention.

[0083] Examples of articles include, but are not limited to, the following articles that can incorporate at least one reinforced textile bonded or adhered according to the present invention, in particular a yarn, cord or textile structure treated with the bonding composition of the present invention applied on the surface of the article to be adhered and / or integrated into the elastomer material of the article; - Belts, in particular drive belts, timing belts, conveyor belts, elevator belts, V-belts. The belt may include yarns or cords embedded in a mass of elastomer or rubber. These belts may similarly include, instead of or in addition to the yarns and cords, a textile structure, in particular a fabric, that adheres to the surface, e.g., the back surface in the case of a drive belt and the back surface and notches in the case of a distribution belt. - Flexible or rigid hoses, in particular brake hoses (including any braided textile structure, single or double braided), hoses, industrial hoses including oil and gas hoses (including a wrapped or spiral textile structure, i.e., a textile structure produced by wrapping or spiraling), hoses (knitted textile structure). Braiding, spiraling, and knitting are generally carried out during the implementation of the pipe by extrusion. - Special items: air springs ("airsprings"), dynamic coupling disks, pipe plugs, compensation / offset seals. - Tires: especially for heavy load carriers and racing.

[0084] Examples of rubber compositions for these articles include the following: drive belts: EPDM or CR based; timing belts: HNBR and CR based; hoses: SBR or EPDM, or NBR / PVC blend or epichlorohydrin or butyl based; air springs: CR based; dynamic disks: CR or NR based; tires: thick parts containing a plurality of mixtures based on NR, BR, or SBR.

[0085] The present invention has the advantage of being integrated into the recovery of renewable non-food raw materials. The present invention enables the recovery of lignin, which is currently a waste from the wood and paper industries. This compound is completely harmless, low-cost, and high-performance. Its use in this situation does not compete with the food market and is not subject to chemical product regulations. This is an agricultural resource.

[0086] Here, the present invention will be described in more detail using embodiments considered as non-limiting examples.

Example

[0087] Part I Preparation of a formulation containing lignosulfonate and an epoxy curing agent (two-component example) The crosslinking or "curing" phenomenon of thermosetting materials, i.e., the formation of a three-dimensional covalent bond network resulting in a reaction product, is accompanied by the release of heat. Therefore, in order to characterize the crosslinking of thermosetting materials, a differential scanning calorimeter (DSC) has conventionally been used. This is achieved by subjecting the uncured thermosetting material to a controlled temperature gradient and then analyzing the location, size, and shape of the resulting exothermic peak.

[0088] Several grams of sodium lignosulfonate (Arbo N18; Tembec N18) and an epoxy curing agent (1,4-butanediol diglycidyl ether) are homogenized for 2 minutes in an aluminum cup under a hood at ambient temperature. The mass ratio of lignosulfonate / epoxy curing agent is precisely 1. Then, several milligrams of this composition are encapsulated in an aluminum crucible with a diameter of 43 mm and a depth of 12 mm. Then, the sample is placed in a DSC3+STAR e SYSTEM DSC facility, and subjected to a temperature gradient of 25 - 300 °C at 10 °C per minute under a nitrogen flow of 80 ml per minute. The total enthalpy change received by the sample is recorded by integrating the surface area under the exothermic peak using STAR SW14.00 software, and then normalized to J·g -1 The firing temperature in °C at which the crosslinking reaction rate is maximum is measured at the maximum peak (peakmax) of the exothermic peak with an accuracy of ±1 °C.

[0089] The same method is applied to produce other compositions containing 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether; diglycidyl 1,2-cyclohexanedicarboxylate; 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate; 1,6-hexanediol diglycidyl ether; glycerol diglycidyl ether; glycerol triglycidyl ether; a mixture of glycerol diglycidyl ether and glycerol triglycidyl ether commercially available from Raschig under the product number GE100; and novolak epoxy resins commercially available from HUNTSMAN under the product number Araldite® PZ323.

[0090] The same method is applied to produce other samples containing only sodium lignosulfonate.

[0091] The same method is applied to produce other samples containing only an epoxy curing agent.

[0092] Table 1

Table 1

[0093] The change in exothermic energy measured for the control sample containing only lignosulfonate is normalized to 100%.

[0094] Compositions containing only an epoxy curing agent (lignosulfonate / hardener mass ratio 0) show zero or low exothermic variations, such as 0 to 33% in relation to the lignosulfonate control.

[0095] A composition containing sodium lignosulfonate and an epoxy curing agent (sodium lignosulfonate / curing agent mass ratio 1) exhibits a heat generation energy variation of 595 - 1199% in relation to the sodium lignosulfonate control. This high heat generation variation in relation to the control is characteristic of the cross - linking or "firing" phenomenon of thermosetting materials. The role of the epoxy curing agent with respect to the sodium lignosulfonate is clearly identified here.

[0096] Example Section II: Preparation Examples of Adhesive Formulations The definitions and measurement or control methods described in this section are generally applicable as required, unless otherwise specified.

[0097] The dry extract (or mass concentration) of the preparation is defined as the percentage of the residual dry matter after evaporating volatile materials (water, solvents) according to a defined drying method. For a wet sample taken with a mass m ech = 2 - 5 grams, analysis is carried out using an analytical balance in a desiccator. Place the sample in a pre - weighed aluminum cup containing a glass fiber filter without binder, with a surface density of 52 g·m -2 and a threshold of 1.6 μm. Then, subject the whole to a temperature of 120 °C until the mass is completely stabilized. The result is expressed in % units.

[0098] The viscosity of the preparation is measured at 23 °C using a Brookfield viscometer. Unless otherwise specified, measurements are made at a speed of 60 rpm (revolutions per minute) using the ULA (Ultra Low Viscosity Adaptator) module and No. 1 mobile (low - viscosity system).

[0099] Measure the pH of the aqueous preparation using a METLER 340 pH meter calibrated for measurements in a basic medium using a buffer solution. Use a glass electrode and 3M KCl electrolyte.

[0100] Unless otherwise described, the water used to make the preparation is reverse osmosis quality water with a residual conductivity of less than 70 μS / cm.

[0101] Example C.II-1: Preparation of an Adhesive Based on Sodium Lignosulfonate and an Epoxy Hardener In a first embodiment of the present invention, 64.2 g of sodium lignosulfonate (Arbo N18; Tembec) is dissolved in 1184 g of water while stirring. Next, 2.5 g of a 10 wt% sodium hydroxide solution is added to the solution, and this is maintained under stirring for 10 minutes to completely solubilize it. This solution is added to 983 g of a styrene-butadiene-vinylpyridine copolymer latex (VPSBR) while stirring. During the hardener preparation stage, the whole is maintained under stirring (150 rpm).

[0102] Take 35 g of GE100 and vigorously stir it with 230 grams of water (300 rpm). This solution is added to the preparation of the lignosulfonate and the latex. Stirring is maintained for several minutes until it is completely homogenized.

[0103] The preparation has a pH of 10.8, a dry extract (solid content) of 19.43% and a viscosity of 2.45 mPa.s.

[0104] By applying the same method and varying the following parameters, two other compositions were produced: Mass ratio of hardener / sodium lignosulfonate: 56% - 116% [Sodium lignosulfonate + hardener] / latex mass ratio: 18% - 21% Mass % of dry latex in the composition: 80 - 84%.

[0105] In total, three compositions were produced.

[0106] Example C.II-2: Second Preparation Method for Preparing a Sodium Lignosulfonate Adhesive and an Epoxy Hardener In the second embodiment of the present invention, 34.8 g of sodium lignosulfonate is introduced into a container, and 782 g of water is gradually added. The solution is stirred at 200 rpm. Then, 20 g of a 10% by mass sodium hydroxide solution and 100.7 g of 20% by mass ammonia are continuously added to the preparation while stirring. The mixture is stirred at 200 rpm for 10 minutes.

[0107] To a latex preparation of styrene-butadiene copolymer (SBR wet latex; 946 g) and 157 g of previously homogenized water, a basic solution of sodium lignosulfonate is added while stirring.

[0108] 75.5 g of GE100 is vigorously stirred (300 rpm), and 383.75 grams of water is added thereto. This emulsion is immediately added to the preparation of lignosulfonate and latex while stirring. Stirring is maintained for several minutes until complete homogenization.

[0109] The preparation has a pH of 12.2, a dry extract of 19.9% and a viscosity of 2.7 mPa·s.

[0110] By applying the same method and varying the following parameters, another composition was produced: Mass ratio of curing agent / sodium lignosulfonate: 217% - 218% [Sodium lignosulfonate + curing agent] / latex mass ratio: 21% - 29% Mass % of dry latex in the composition: 78% - 82%.

[0111] In total, two compositions were produced.

[0112] Example C.II - 3: A third preparation method for preparing an adhesive based on sodium lignosulfonate and an epoxy curing agent In the third preparation method of the present invention, 19 g of sodium lignosulfonate is dissolved in 955 g of water with stirring, and 19 g of a 10% by mass sodium hydroxide solution is added to prepare a basic solution of sodium lignosulfonate. To completely solubilize, the preparation is left under stirring at 200 rpm for 10 minutes.

[0113] A basic latex dispersion is prepared by introducing 167 g of water into the container, and then this is stirred at 200 rpm. Then, 1049 g of styrene-butadiene copolymer latex (SBR) and then 25 g of a 20% by mass ammonia solution are continuously introduced. Then, the basic lignosulfonate solution is added to the latex dispersion with stirring.

[0114] 49 g of GE100 is vigorously stirred (300 rpm), and 216 grams of water is added thereto. This solution is immediately added to the preparation of lignosulfonate and latex with stirring. Stirring is maintained for several minutes until complete homogenization.

[0115] The preparation has a pH of 12.25, a dry extract of 18.33% and a viscosity of 2.25 mPa·s.

[0116] By applying the same method and varying the following parameters, two other compositions were produced: Mass ratio of curing agent / lignosulfonate: 255% - 516% [Lignosulfonate + curing agent] / latex mass ratio: 16% - 46% Mass % of dry latex in the composition: 68% - 86%.

[0117] In total, three compositions were produced.

[0118] Example C.II-4: Fourth preparation method for preparing an adhesive based on potassium lignosulfonate and an epoxy curing agent In this preparation method, 94.5 g of an aqueous potassium lignosulfonate solution is mixed with 63.7 g of GE100. Then, while stirring vigorously, 1794.8 g of water is poured into the mixture. Thereafter, 33 g of a 10% by mass sodium hydroxide solution and 166.6 g of a 20% by mass ammonia solution are continuously added to the preparation while stirring. The mixture is left under stirring for 10 minutes and then added to a chloroprene latex (wet latex CR; 1004 g) in water (176 g) while stirring.

[0119] The preparation has a pH of 12.69, a dry extract of 19.58% and a viscosity of 2.45 mPa·s.

[0120] The same method was applied to produce two other compositions by varying the following parameters: Mass ratio of hardener / lignosulfonate: 33% - 134% [Mass ratio of [lignosulfonate + hardener / latex]]: 20% - 47% Mass % of dry latex in the composition: 65% - 79%.

[0121] In total, three compositions were produced.

[0122] Example C.II - 5: A fifth preparation method for preparing an adhesive based on potassium lignosulfonate and an epoxy hardener In this preparation method, 94.5 g of an aqueous potassium lignosulfonate solution is mixed with 63.7 g of GE100. Then, while stirring vigorously, 1794.8 g of water is poured into the mixture. Thereafter, 33 g of a 10% by mass sodium hydroxide solution and 166.6 g of a 20% by mass ammonia solution are continuously added to the preparation while stirring. The mixture is left under stirring for 10 minutes and then added to a dispersion of chloroprene latex (wet latex CR; 1004 g) in water (176 g) while stirring.

[0123] 1306 g of this preparation is taken and diluted in 996 g of water while stirring. Next, 36 g of a 55% by mass zinc oxide aqueous dispersion, 78 g of a 35% by mass carbon black aqueous dispersion, and 83 g of an adhesion promoter (block isocyanate) are continuously added while gently stirring.

[0124] The preparation has a pH of 12.32, a dry extract of 14.1%, and a viscosity of 1.95 mPa·s.

[0125] By applying the same method and varying the following parameters, two other compositions were produced: Mass ratio of hardener / lignosulfonate: 33% - 135% [Lignosulfonate + hardener] / latex mass ratio: 20% - 47% Mass % of dry latex in the composition: 48% - 59%.

[0126] In total, three compositions were produced.

[0127] The compositions of these examples are used in the part regarding the treatment of reinforced textiles.

[0128] Section III - Treatment of Reinforced Textiles The definitions and measurement or control methods described in this section are generally applicable as required, unless otherwise specified. The mechanical properties of the treated textiles, such as tensile strength at break, tensile elongation at break, shrinkage, thermal shrinkage, contraction (vapor shrinkage), thermal shrinkage force, linear weight, loading rate (dip pick-up; DPU), stiffness, etc., are measured according to the standards effective in the textile industry. In relation to the present invention, it has been confirmed that the new treatment does not bring about any change in these properties compared to the standard RFL.

[0129] The adhesive preparation of the present invention is evaluated for its adhesion performance. After coating the textile, the textile is placed within an unvulcanized rubber matrix such that the surface of the textile in contact with the rubber remains free from any contamination. Thereafter, the matrix containing the textile is vulcanized by compression according to the temperature, time and pressure specific to each rubber. The assembly of textile + vulcanized matrix forms an adhesion test specimen.

[0130] The adhesion test specimens can take a plurality of forms described in various international standards such as ISO 36:2017. The tests carried out on the specimens and thus for determining adhesion are generally known to those skilled in the art by names such as the T - test ("pull - out test", ASTM D2229 - 04), the H - test (in accordance with the NF ISO 4647 standard or ASTM D4776 - 04), peel (peel test), etc. Next, the test is carried out by applying stress to the specimen until the interfacial contact zone of the tear of the textile or the tear of the rubber matrix breaks. Thereafter, the adhesion is evaluated according to criteria such as the appearance of the textile at break, the maximum adhesion force, which may in some cases be attributed to the thickness of the test specimen, the average tear force, etc.

[0131] General information about the impregnation method Generally, the textile impregnation method is carried out by dipping (dipping, soaking) within a tank storing the adhesive preparation. A scheme of such a method is illustrated in Gomes A., Nabih N., Kramer T, Adhesion activation of tire textiles by resorcinol formaldehyde free coatings, Rubber World, March 2016.

[0132] Coils of untreated yarns, cords and cables are positioned on creels at the line inlet. An accumulator system may optionally be used. The yarns, cords and cables can be directly immersed in a tank for the application of the bonding composition or impregnated with kiss rolls. After immersion or impregnation, the excess wet preparation is preferably removed, for example, by pressing (padding), suction or foaming.

[0133] Next, drying and / or crosslinking of the bonding composition is carried out. In this way, the coated and impregnated textile can be passed through an oven, enabling drying and crosslinking of the bonding composition. After removal from the oven, the textile can be subjected to the impregnation step again and then passed through the oven, and these steps can be repeated, especially up to a total of 4 impregnations (2, 3 or 4 times). After leaving the line, the yarn, cord or cable can be wound up on a winder.

[0134] In another impregnation method, which is particularly suitable for mineral fibers (such as glass, basalt, carbon), a unwinding system composed of combs and / or "pigtails" can be used at the exit of the creel. This enables maximum fibrillation of the multifilament yarn and promotes thorough impregnation. After the impregnation and drying and / or crosslinking steps, the yarn is then twisted in the line. The twisting is preferably carried out on the already treated yarn. Additional processing processes can be carried out on the cord thus formed.

[0135] In various different methods, the speed can be in the range of 1 m / min to 150 m / min, and the temperature of the oven is in the range of 30°C to 350°C, more specifically 100 to 300°C, and even more specifically 140 to 220°C. It is also possible to apply mechanical tension to the textile. Unless otherwise indicated, in the following examples, the textile was treated with the bonding composition which is the subject of the present invention under the same conditions as those applied during the treatment with RFL.

[0136] Example III-1: Treated polyamide 4-6 reinforcing material for belts In one preparation example of the present invention, the inventors aim to present one solution that can be used as a reinforcing material in assemblies such as drive belts or conveyor belts.

[0137] For this purpose, a cord made of PA4-6 with a 470 / 5×3 dtex (100 / 125) configuration was constructed using the successive steps of twisting and then cabling. The resulting cord was treated by a first impregnation in a solution of methylene diphenyl diisocyanate in toluene and then subjected to drying and heat curing in an oven. Next, instead of the usually applied RFL treatment, the cord was impregnated in a tank storing the bonding composition (adhesive) of the present invention with a dry matter concentration of 20% by mass. The various different yarns impregnated with the various different adhesives obtained were evaluated for adhesion to a peroxide-accelerated EPDM (ethylene-propylene-diene monomer)-based mixture. Test specimens were produced by compression molding. It was possible to obtain control adhesion values with the RFL-impregnated yarns produced under the same conditions. The adhesion values obtained are presented in Table 2 and are expressed as the percentage of adhesion in relation to the adhesion obtained with the control RFL yarns.

[0138] Example III-2; Treated glass reinforcing material for profiles In one preparation example of the present invention, the inventors aim to present one invention that can be used as a reinforcing material in seals and profiles such as window or door seals. Such a reinforcing material is made of a glass yarn containing a glass fiber sizing agent that must be compatible with the bonding composition.

[0139] To do this, several E-glass yarns of 136 tex strength were subjected to a beam-breaking process and impregnation in a tank containing the bonding composition (adhesive) of the present invention instead of RFL. In this example, an adhesive having a mass concentration of 20% was evaluated. The impregnated yarns were subjected to drying and heat curing in an oven. After being taken out of the oven, the yarns were subjected to a twisting operation to impart 135 turns per meter in the Z direction to the yarns. Next, three impregnated twisted yarns were cabled together in one direction at the 135S level.

[0140] The various yarns impregnated with the obtained various adhesives were evaluated for adhesion to an EPDM rubber mixture that has been carried out by conventional extrusion processing. Test pieces were produced by compression molding. It was possible to obtain control adhesion values with yarns impregnated with RFL produced under the same conditions. The obtained adhesion values are presented in Table 2 and are expressed as the percentage of adhesion in relation to the adhesion obtained with the control RFL yarns.

[0141] Example III-3: Treated polyethylene terephthalate reinforcement for pipes In another preparation example of the present invention, the inventors aim to present one solution that can be used as a braided, coiled, lapped or knitted reinforcement in a brake pipe.

[0142] Example III-3(a): For this purpose, a 90Z twisted yarn was applied to a polyethylene terephthalate (PET) yarn having a strength of 1100 dtex. The resulting yarn was subjected to an impregnation process in a bonding composition (adhesive) which is the subject of the present invention, followed by treatment by heat curing in an oven. The adhesive used in this example has a dry matter or solid concentration of 20%. Various different yarns impregnated with the adhesive were evaluated for adhesion to an EPDM rubber blend accelerated with a peroxide conventionally used in brake pipes. Test specimens were produced by compression molding. It was possible to obtain a control adhesion value with a yarn impregnated with RFL produced under the same conditions. The obtained values are presented in Table 2 and are expressed as the percentage of adhesion in relation to the adhesion obtained with the control RFL yarn.

[0143] Example III-3(b): In another example, a cord having a configuration of 830 / 2×3 dtex was constructed using the successive steps of twisting and then cabling. The resulting cord was treated by a first impregnation in a solution of methylene diphenyl diisocyanate in toluene, followed by drying and heat curing in an oven. The bonding composition (adhesive) used in this example has a dry matter or solid concentration of 20%. Various different yarns impregnated with the adhesive were evaluated for adhesion to a CR-based rubber mixture. Test specimens were produced by compression molding. It was possible to obtain a control adhesion value with a yarn impregnated with RFL produced under the same conditions. The obtained values are presented in Table 2 and are expressed as the percentage of adhesion in relation to the adhesion obtained with the control RFL yarn.

[0144] Table 2

Table 2

[0145] The polyamide 4-6 cords of Example II1-1 treated with various different adhesives of Example C.11-1 showed satisfactory adhesion levels to EPDM compared to the control yarns impregnated with RFL. Observation of the resulting adhesion levels as well as the fracture patterns indicates that the adhesives evaluated are compatible with the first impregnation applied to the textile.

[0146] The E-glass cords of Example III-2 treated with various different adhesives of Example C.II-2 showed satisfactory adhesion levels to EPDM compared to the control yarns impregnated with RFL. This level is lower than that obtained with RFL, but is high enough to ensure effective performance of the application. Observation of the resulting adhesion levels as well as the fracture patterns indicates that the adhesives evaluated are compatible with the sizing agent of the glass. Furthermore, the glass yarns treated in this way showed no visual damage and did not cause excessive contamination on the processing line. This indicates that the adhesives under evaluation have the ability to impart the same properties as RFL, including mechanical protection properties.

[0147] The PET yarns of Example III-3(a) treated with each of the various different adhesives of Example C.II-3 showed higher adhesion levels to EPDM compared to the control yarns impregnated with RFL. The PET yarns of Example III-3(b) treated with each of the various different adhesives of Example C.II-4 showed satisfactory adhesion levels to the CR mixture compared to the control yarns impregnated with RFL.

[0148] As a conclusion, the results of these various tests clearly demonstrate that the adhesive composition according to the invention constitutes a very advantageous alternative to the use of conventional RFL adhesive solutions containing formaldehyde and resorcinol.

Claims

**Claim 1** A bonding composition for textiles, comprising a lignosulfonate, an epoxy curing agent for this salt containing at least two epoxy units, and an elastomeric latex. **Claim 2** The composition according to claim 1, wherein the lignosulfonate is sodium lignosulfonate, potassium lignosulfonate, magnesium lignosulfonate, ammonium lignosulfonate or calcium lignosulfonate. **Claim 3** The composition according to claim 1 or 2, wherein the curing agent is selected from diglycidyl or polyglycidyl ethers of aliphatic polyols; diglycidyl or polyglycidyl ethers of polyfunctional phenols; polyglycidyl ethers of condensation products of formaldehyde and phenol obtained under acidic conditions; di- or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids; compounds containing epoxycyclohexyl groups; polyepoxy compounds obtained as a result of epoxidation of olefinically unsaturated compounds; and mixtures thereof. **Claim 4** The composition according to claim 3, wherein the curing agent is selected from the following compounds: 1,4-butanediol diglycidyl ether; 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether; diglycidyl 1,2-cyclohexanedicarboxylate; 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate; 1,6-hexanediol diglycidyl ether; glycerol diglycidyl ether; glycerol triglycidyl ether; a mixture of glycerol diglycidyl ether and glycerol triglycidyl ether; novolak-type epoxy resins and mixtures thereof. **Claim 5** The composition according to any one of claims 1 to 4, comprising a latex of acrylonitrile / carboxylated butadiene copolymer (XNBR), a latex of acrylonitrile / hydrogenated butadiene (HNBR), a latex of chlorosulfonated polyethylene (CSM), a latex of styrene-butadiene-vinylpyridine copolymer (VPSBR), a latex of styrene / butadiene copolymer (SBR), a latex of acrylonitrile / butadiene copolymer (NBR), a latex of polybutadiene (BR), a latex of chlorobutadiene (CR), a natural rubber latex (NR), a polyurethane latex, or a mixture of at least two thereof.

6. The composition according to any one of claims 1 to 5, wherein the mass content of the dry matter of the composition can be approximately 2 to approximately 38%, more particularly approximately 4 to approximately 30%, and even more particularly approximately 7 to approximately 25%.

7. The composition according to any one of claims 1 to 6, comprising approximately 40 to approximately 95% by weight, preferably approximately 55 to approximately 90% by weight of elastomer in relation to the composition.

8. The composition according to any one of claims 1 to 7, wherein the mass ratio of the curing agent / lignosulfonate is approximately 0.01 to approximately 5, more particularly approximately 0.03 to approximately 1, and typically approximately 0.05 to approximately 0.

5.

9. The composition according to any one of claims 1 to 8, wherein the [curing agent + lignosulfonate] / latex mass ratio is approximately 0.05 to approximately 0.6, more particularly approximately 0.15 to approximately 0.

5.

10. The composition according to any one of claims 1 to 9, having a neutral or basic pH, more particularly approximately 7 to approximately 13, and even more particularly approximately 9 to approximately 13.

11. A kit for producing the bonding composition according to any one of claims 1 to 10, comprising a first composition containing a lignosulfonate and an elastomer latex, and a second composition containing an epoxy curing agent of the lignosulfonate containing at least two epoxy units.

12. Use of the composition or kit according to any one of claims 1 to 11 for imparting adhesion properties to a reinforcing textile in relation to rubber.

13. A reinforced textile, in particular a yarn, cord or textile structure, at least partially coated and / or impregnated with the bonding composition according to any one of claims 1 to 10.

14. A rubber or rubber-containing part, wherein the rubber incorporates at least one reinforced textile according to any one of claims 1 to 13 on and / or within the surface of the rubber.

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